The self-assembly of a [Ga4L6]12- tetrahedral cluster Thermodynamically driven by host-guest interactions
The self-assembly of a [Ga4L6]12- tetrahedral cluster Thermodynamically driven by host-guest interactions
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DOI：
10.1021/ic0102283
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发表时间：
2001-09-24
影响因子：
4.6
通讯作者：
Raymond, KN
中科院分区：
文献类型：
--
作者：
Johnson, DW;Raymond, KN
描述了一种预测设计策略引起的[Ga4L6]（12-）四面体金属配体簇的客诱导合成。六种双二十烯酰胺配体中的每一种都跨越分子四面体的边缘，在顶点处有四个Ga（III）离子。小的阳离子物种不仅占据了团簇内部的大空隙体积（约300-400埃(3)），而且通过形成主客体复合物驱动团簇组装是必要的热力学同盟。NMe4+、NEt4+和NPr4+都符合这一目的，此外，团簇对这三种客体的结合表现出偏好：根据H-1核磁共振光谱，NEt4+的结合强度是NPr4+的300倍，而NPr4+的结合强度又是NMe4+的4倍。K-6(NEt4)(6)[Ga4L6]簇通过核磁共振谱、高（傅里叶变换离子回旋共振，FT-ICR）和低分辨率电喷雾电离（ESI）质谱、元素分析和单晶x射线衍射进行了表征。在固态结构中证实了NEt4+客体分子的结合，这表明该分子在固态中含有较大的通道。这一结果表明，客体分子将在更大的预先设计的金属配体簇的形成中发挥越来越大的作用。
The guest-induced synthesis of a [Ga4L6](12-) tetrahedral metal-ligand cluster resulting from a predictive design strategy is described. Each of the six dicatecholamide ligands spans an edge of the molecular tetrahedron with four Ga(III) ions at the vertices. Small cationic species not only were found to occupy the large void volume (ca. 300-400 Angstrom (3)) inside this cluster but also are necessary thermodynamic ally to drive cluster assembly via formation of a host-guest complex. NMe4+, NEt4+, and NPr4+ all suit this purpose, and in addition the cluster exhibits a preference in the binding of these three guests: NEt4+ is bound 300 times more strongly than NPr4+, which is in turn bound 4 times more strongly than NMe4+, as determined by H-1 NMR spectroscopy. The K-6(NEt4)(6)[Ga4L6] cluster was characterized by NMR spectroscopy, high- (Fourier transform ion cyclotron resonance, FT-ICR) and low-resolution electrospray ionization (ESI) mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. The binding of the NEt4+ guest molecule was confirmed in the solid state structure, which reveals that the molecule contains large channels in the solid state. As this result exemplifies, it is suggested that guest molecules will play an increasing role in the formation of larger, predesigned metal-ligand clusters.